6/.

Electronic Spectroscopy of Transition Metal Complexes

a/. Introduction The Table

4 5 6 7 8 9 10 11
 The TM Elements

4 5 6 7 8 9 10 11
1st row Ti V Cr Mn Fe Co Ni Cu

Coinage Metals
2nd row Zr Nb Mo Tc Ru Rh Pd Ag

3rd row Hf Ta W Re Os Ir Pt Au
Platinum group metals

Early TM Middle TM Late TM

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Stories of elements written by experts
 • Many compounds of transition metals have colors. Main group metal
compounds are usually colorless.

• The colors are usually gentle rather than vivid – weak rather than
strong

• Some metal ions have typical colors, e.g. many copper(II) compounds
are blue, those of nickel(II) are green, manganese(II) compounds are
only weakly colored, and a wide range of colors are associated with
the different oxidation states of vanadium.

CuSO4•5H2O NiCl2ꞏ6H2O FeCl3•6H2O FeCl2•4H2O CoCl2ꞏ6H2O

Transition metal ions especially chromium(III) are responsible for
the colors of gemstones

Ruby
Al2O3:Cr(III)

(Be3Al2(SiO3)6): Cr(III)
Quartz (SiO2) which has some Si atoms 
replaced with Fe(IV) ion Amethyst

O
IV
Fe
O
O
O

t2

High spin d4

Origin of the deep purple color?
 Stained glass

Plastocyanin – a copper
electron transfer protein
 Origin of Colors

Visible region

R O Y G B V
IR UV

600 nm 500 nm 400 nm

Wavelength

Wavelength range (nm) color Complementary color

< 400 nm Ultraviolet
400 – 450 nm Violet Yellow
450 - 490 Blue Orange
490 - 550 Green Red
550 - 580 Yellow Violet
580 - 650 Orange Blue
650- 700 Red Green

Color of a material is the visible light that it does not absorb

UV-vis absorption spectra of photosynthetic pigments
UV-vis Absorption (Electronic) Spectroscopy
I0 I

Source L detector
Sample
(solution or solid)

IoI
A
l
o
g

L
c
  ε 
Beer-Lambert Law

A = Absorbance
I0 = intensity of light before passing through the sample
I = intensity of light after absorption
 = molar absorptivity or molar extinction coefficient; unit = M-1cm-1
L = optical path (for solution sample, L usually = 1 cm)
c = concentration of the sample; unit = M
 Electronic Transition

Atoms – Atomic orbitals

Electronic transitions from a lower energy orbital to higher energy

empty orbitals give rise to atomic absorption

e.g. Na atom Atomic Absorption Spectrum of Na atom

Electronic configuration 1s2 2s2 2p6 3s1 3s3p

5p
3s5p
4p 3s4p

3p

3s
Similarly, for molecules, absorption of UV-vis light of correct frequency
(energy) leads to excitation of electron from one molecular orbital to a
higher energy molecular orbital.

h

Ground State Excited State

The state of a molecule (or atom) is defined by its electronic configuration
(arrangement of electrons in different orbitals). Ground state and excited
state have different electron configurations and hence different energies.
Ground state is the most stable electronic configuration. A precise
definition of electronic transition is transition of a molecule from its ground
state to an excited state by absorption of a photon
 UV‐vis absorption bands are broad: 
The ground state Depending on the extent of excited
and excited states state distortion, absorption
can be represented excited state bandwidth can range from 100 cm-1
by potential energy to ~5000 cm-1
curves = 6
= 5
= 4 Absorption bands arising from 
n = nth vibration level 
in the excited state = 3 transition from ground state to an 
= 2
excited state are broad. The lowest 
energy transition is = 0*=0 
= 1
= 0
n= nth vibration level 
in the ground state
= 0*=4 
= 0*=3 
= 0*=5 
= 0*=2 

Extinction coefficient
= 6
= 0*=6 
= 5
= 0*=1 
= 4
= 3 = 0*=7 
= 0*=0 
= 2
ground state = 1
= 0

Wavelength (nm)
Nuclear configuration
 c
UV-vis Absorption Spectrum

E
h
x-axis : wavelength (nm) or wavenumber (cm-1)
y-axis : , molar absorptivity (M-1cm-1)
 

Absorption maxima/peak (max)

max
Cu2+

 Absorption band

cm-1

Wavelength (nm)
 b/. Origins of Colors of Transition Metal Complexes

i/. d-d / crystal field / ligand field transition

Consider an octahedral d1 complex e.g. Ti(H2O)63+

OH2 3+ eg eg
H 2O OH2
Ti
H 2O OH2
OH2 t2g t2g

d1
In systems that have only 1 electron (i.e. d1), the symmetry of the orbitals is equal to
the symmetry of State

2T 2E The superscript is spin multiplicity

2g g = 2S+1 (S = total spin). For d1, S = 1/2,
spin multiplictiy = 2(1/2) +1 = 2 (doublet)
Capital letter for the
symmetry of state
The solution of Ti(H2O)63+ is purple and its UV-vis absorption shows a
very weak absorption at 500 nm (max ~ 5 M-1cm-1)

2T 2E
2g g

5,000 10,000 15,000 20,000 25,000 30,000

cm-1
Ti3+(d1) Mn2+(d5)

V3+(d2)

Fe2+(d6)
d1, d4, d6, d9 – 1 band

Cr3+(d3) Co2+(d7) d2, d3, d7, d8 – 2 - 3 bands

(due to interelectronic
repulsion, there are more
Ni2+(d8)
than 1 d-d excited state,
and hence more than 1
absorption band)

Cu2+(d9)
d5 - very weak bands

Cr2+(d4)
UV-vis Absorption Spectra of Ruby and Emerald (c.f. the spectrum of
[Cr(H2O)6]3+)
ii/. Charge-transfer transition

Fully allowed transition Me

Me
Intense ( = 103 – 104 M-1cm-1)
N
N
N
Cu+

Me N

Me
red

*-orbital of ligand

h

3d orbitals of Cu

Cu+ 3d10

No d-d transition but a strong absorption in the visible region which

is due to metal-to-ligand-charge-transfer (MLCT) transition
 Copper(I) template formation of interlocking molecules

Jean Pierre Sauvage (2016

Nobel prize for chemistry)

Cu(I) Cu(II)
 O
Ligand-to-Metal-Charge-Transfer (LMCT) Transition

Mn7+
O
O
O
Mn7+ - d0, no d-d transition. But the UV-vis
absorption spectrum of permanganate ion
display two very intense bands in the visible
region. The solution of permanganate ion has
a distinct deep purple color.

d-orbitals of Mn(VIII)

Wavenumber (cm-1)
h Electronic
configuration of
LMCT excited
Electronic state
configuration of
ground state
Lone-pairs of O
atoms
 Metal-to-Ligand-Charge-Transfer (MLCT) Transition

2+

N d d
N N
Ru
N N of bipy
N of bipy
LUMO

Metal-to-ligand-
Ru(bipy)32+ Charge-Transfer
(MLCT) transition
h

N N

bipy = 2,2’-bipyridine

Because of the extended HOMO d d

-conjugation, the ligand 1MLCT
bipy has low-lying *- ground state
orbitals – stronger -back Singlet MLCT excited state
bonding
 MLCT Absorption of Ru(bipy)32+

max = 452 nm

max = 1.4 x104 M-1cm-1

MLCT band

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 2+ 2+

N N -
N 2+ N h N 3+ N
Ru Ru
N N N N
N N

•The photoexcitation creates a MLCT excited state that formally consists of a

Ru(III) and a 1-electron reduced bipy ligand.

•The MLCT excited state of Ru(bipy)32+ is emissive: MLCT luminescence.

 Electroluminescence from MLCT excited state of Ir(ppy)3 - OLED

Ir(ppy)3

Mark E. Thompson
 Trends in Charge Transfer Transitions
(a) Metal-to-Ligand-Charge-Transfer (MLCT)
For complexes having the same ligands, moving down the group, the MLCT
transition energy decreases
2+ 2+
MLCT decreases down the group

N N

8 N
N
Ru
N
N
>
N
N
Os
N
N
N N

max = 522 nm
max = 452 nm
Ru * orbital of bipy

Os
energy

5d orbital
4d orbital of Ru is lower in energy than
5d orbital of Os: energy gap between
4d orbital 4d of Ru and * of bipy > energy gap
between 5d of Os and * of bipy
 (b) Ligand-to-Metal-Charge-Transfer (LMCT)

For complexes having the same ligands, moving down the group, the LMCT
transition energy increases
LMCT increases down the group

7 <
<
Mn
max 528 nm 286 nm 227 nm

Tc 5d orbital of Re(VIII)
4d orbital of Tc(VIII)

Re 3d orbital of Mn(VIII)
energy

Lone pair orbital of O

 (b) Ligand-to-Metal-Charge-Transfer (LMCT)

For complexes having same metal ion but different ligands from the same group
LMCT decreases down the group

17 > >

Cl
3d orbital of Co(II)

Br

I
energy

Lone pair orbital of I (5p)

Lone pair orbital of Br (4p)

Lone pair orbital of Cl (3p)

 (b) Ligand-to-Metal-Charge-Transfer (LMCT)

For isostructural and isoelectronic complexes having the same ligands, LMCT energy
decreases as oxidation state of metal ion increases

> > Mn7+

O
O
O
K2CrO4 KMnO4
max 445nm 525 nm 640 nm

LMCT energy decreases

3d orbital of V(V) 3d orbital of Cr(VI)
V Cr Mn
3d orbital of Mn(VII)
energy

Lone pair orbital of O